US10320041B2 - Zinc-air battery surfactants - Google Patents

Zinc-air battery surfactants Download PDF

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US10320041B2
US10320041B2 US15/518,751 US201515518751A US10320041B2 US 10320041 B2 US10320041 B2 US 10320041B2 US 201515518751 A US201515518751 A US 201515518751A US 10320041 B2 US10320041 B2 US 10320041B2
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zinc
ppm
electrolyte
air battery
anode
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US20170237134A1 (en
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Abhishek GUHA
Marc SYVERTSEN
Tony M. RUBSAM
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Energizer Brands LLC
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Energizer Brands LLC
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Assigned to JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT reassignment JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT PATENT SECURITY AGREEMENT Assignors: ENERGIZER AUTO, INC., ENERGIZER BRANDS, LLC
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/045—Cells with aqueous electrolyte characterised by aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y02E60/128—

Definitions

  • FIG. 3 is a wireless streaming pulse discharge curve comparison between a control anode (containing a control surfactant) and an anode containing 4000 ppm of an amphoteric fluorosurfactant at 4-month room temperature delay, according to the examples.
  • Representative substituted cycloalkyl groups may be mono-substituted or substituted more than once, such as, but not limited to: 2,2-; 2,3-; 2,4-; 2,5-; or 2,6-disubstituted cyclohexyl groups or mono-, di-, or tri-substituted norbornyl or cycloheptyl groups, which may be substituted with, for example, alkyl, alkoxy, amino, thio, hydroxy, cyano, and/or halo groups.
  • halogen refers to bromine, chlorine, fluorine, or iodine. In some embodiments, the halogen is fluorine. In other embodiments, the halogen is chlorine or bromine.
  • anionic fluorosurfactants refers to fluorosurfactants containing anionic groups and/or groups able to be deprotonated into anionic groups.
  • the anionic fluorosurfactant comprises carboxy group(s), sulfonic group(s), phosphate group(s), phosphonate group(s) or their corresponding salts.
  • amphoteric fluorosurfactants and surfactants of Formula (II) provide for improvements in the operating voltage of such batteries when operated at high drain rates, such as those encountered during pulsed discharge. Improvements in voltage eliminate, or at least substantially decrease, the occurrence of low battery signals. It is believed that this effect is provided by increasing the operating voltage relative to the cut-off voltage of the battery.
  • amphoteric fluorosurfactants or surfactants of Formula (II) are included in the anode (i.e. negative electrode) side of the battery. Without being bound by theory, it is believed that the amphoteric fluorosurfactants or surfactants of Formula (II) interact with the zinc in the anode thereby significantly raising the operating voltage of the battery, as compared to a battery employing a control surfactant (i.e. a non-fluorinated surfactant or not of Formula (II)).
  • the higher operating voltage allows for the zinc-air battery anode to exhibit better performance characteristics than a control battery (i.e. one without the amphoteric fluorosurfactant or surfactants of Formula (II)), particularly when the batteries are discharged under pulsed conditions to higher end points.
  • amphoteric fluorosurfactant reduces voltage suppression while maintaining gassing reliability.
  • R 13 , R 14 , R, R 16 , R 17 , R 18 , R 19 , R 20 , and R 21 are each independently a hydrogen, alkyl, alkenyl, or cycloalkyl group; X 2 is O or S; X 3 is OH or SH; and w is 5-50. In some embodiments, R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , and R 21 are each hydrogen. In some embodiments, X 2 is O. In some embodiments, X 3 is OH. In some embodiments, w is 5-15. In some embodiments, w is 5-10.
  • R 10 , R 11 , R 12 , and R 13 are each independently a hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or substituted or unsubstituted cycloalkyl group; and m is 100-500.
  • R 10 , R 11 , R 12 , and R 13 are each hydrogen.
  • m is 100-200.
  • R 10 , R 11 , R 12 , and R 13 are each hydrogen and m is 100-200.
  • the anode is prepared by a two-step process (a) dry zinc blending and (b) electrolyte preparation.
  • the blended zinc may be dispensed into the anode can cavity followed by the electrolyte in set proportions which may vary as per cell size.
  • the dry zinc blending step includes admixing zinc or zinc alloy, a gelling agent, and a corrosion inhibitor.
  • a small concentration of water may be added to the admixture to facilitate blending and the water may be subsequently dried off.
  • porous diffusion layer 57 is a microporous hydrophobic polymeric material such as a polytetrafluoroethylene (PTFE) membrane about 25 to about 100 microns thick, which permits passage of air through and which is generally impervious to battery electrolyte.
  • PTFE polytetrafluoroethylene
  • the porous diffusion layer 57 is TeflonTM.
  • the porous diffusion layer 57 in combination with the air ports 54 , is used to efficiently transport oxygen to the active reaction surface area of the cathode assembly.
  • Embodiment E The zinc-air battery of any one of Embodiments A-D, wherein the amphoteric fluorosurfactant is present in the electrolyte from about 3000 ppm to about 12000 ppm.
  • Embodiment F The zinc-air battery of any one of Embodiments A-E, wherein the electrolyte further comprises a surfactant that is hexyl diphenyl oxide disulfonic acid, diethylenetriamine, octylphenoxypolyethoxyethanol, a compound of Formula (III), or a combination of any two or more thereof; and the compound represented as Formula (III) is:
  • Embodiment FF The zinc-air battery of any one of Embodiments AA-EE, wherein the surfactant of Formula (II) is present in the electrolyte from about 3000 ppm to about 12000 ppm.
  • Embodiment GG The zinc-air battery of any one of Embodiments AA-EE, wherein the electrolyte further comprises a second surfactant that is hexyl diphenyl oxide sulfonic acid, diethylenetriamine, an amphoteric fluorosurfactant, or a combination of any two or more thereof.
  • a second surfactant that is hexyl diphenyl oxide sulfonic acid, diethylenetriamine, an amphoteric fluorosurfactant, or a combination of any two or more thereof.
  • Embodiment MM The zinc-air battery of any one of Embodiments AA-LL further comprising a separator between the air cathode and the zinc anode.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently a hydrogen, alkyl, alkenyl, or cycloalkyl group;
  • X 1 is O or S;
  • X 2 is OH or SH; and
  • n is 5-50.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hybrid Cells (AREA)
US15/518,751 2014-10-15 2015-10-14 Zinc-air battery surfactants Active 2035-11-01 US10320041B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/518,751 US10320041B2 (en) 2014-10-15 2015-10-14 Zinc-air battery surfactants

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201462064269P 2014-10-15 2014-10-15
US201462064241P 2014-10-15 2014-10-15
PCT/US2015/055603 WO2016061276A1 (en) 2014-10-15 2015-10-14 Zinc-air battery surfactants
US15/518,751 US10320041B2 (en) 2014-10-15 2015-10-14 Zinc-air battery surfactants

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US20170237134A1 US20170237134A1 (en) 2017-08-17
US10320041B2 true US10320041B2 (en) 2019-06-11

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US (1) US10320041B2 (pt)
EP (1) EP3207586B1 (pt)
JP (1) JP6667515B2 (pt)
CN (1) CN107112547B8 (pt)
AU (1) AU2015332523B2 (pt)
BR (1) BR112017007758B1 (pt)
WO (1) WO2016061276A1 (pt)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3166171B1 (de) * 2015-11-05 2020-02-26 VARTA Microbattery GmbH Elektrochemische zelle
CN110010982A (zh) * 2018-01-05 2019-07-12 苏州宝时得电动工具有限公司 电池
US11437655B2 (en) * 2018-03-15 2022-09-06 Energizer Brands, Llc Long-chain surfactants for improving battery performance
US20200194738A1 (en) * 2018-12-14 2020-06-18 Energizer Brands, Llc Zinc-air electrochemical cells with carbon dioxide scavengers
CA3124821A1 (en) 2018-12-27 2020-07-02 Energizer Brands, Llc Metal-air cells with minimal air access
US11450847B2 (en) * 2019-01-23 2022-09-20 Energizer Brands, Llc Alkaline electrochemical cells comprising increased zinc oxide levels
JP7510081B2 (ja) * 2020-10-01 2024-07-03 日本電信電話株式会社 金属空気電池
US11575168B2 (en) 2021-07-01 2023-02-07 Energizer Brands, Llc Metal-air cells with minimal air access
CN114792780A (zh) * 2022-03-16 2022-07-26 山东合泰新能源有限公司 含有组合锌缓蚀剂的锌电极及其应用的锌镍电池

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Publication number Publication date
CN107112547B8 (zh) 2019-10-01
BR112017007758B1 (pt) 2022-03-22
AU2015332523B2 (en) 2020-05-21
AU2015332523A1 (en) 2017-06-01
EP3207586A4 (en) 2018-03-28
JP2017531295A (ja) 2017-10-19
WO2016061276A1 (en) 2016-04-21
EP3207586A1 (en) 2017-08-23
CN107112547A (zh) 2017-08-29
US20170237134A1 (en) 2017-08-17
CN107112547B (zh) 2019-08-16
BR112017007758A2 (pt) 2018-06-19
EP3207586B1 (en) 2019-11-20
JP6667515B2 (ja) 2020-03-18

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